The disclosed embodiments includes a process for producing hydrogen, comprising the steps of: (a) gasifying a fuel into a raw synthesis gas comprising CO, hydrogen, steam and sulfur and halide contaminants in the form of H2S, COS and HX, where X is a halide; (b) passing the raw synthesis gas through a water gas shift reactor (WGSR) into which CaO and steam are injected, the CaO reacting with the shifted gas to remove CO2, sulfur and halides in a solid-phase calcium-containing product comprising CaCO3, CaS and CaX2; (c) separating the solid-phase calcium-containing product from an enriched gaseous hydrogen product; and (d) regenerating the CaO by calcining the solid-phase calcium-containing product at a condition selected from the group consisting of: in the presence of steam, in the presence of CO2, in the presence of synthesis gas, in the presence of H2 and O2, under partial vacuum, and combinations thereof.
The fuel could be coal, biomass, oil sands, coke, tar, wax oil shales, or combinations of these materials.
Although the steam may be injected into the WGSR in any functional quantity, it is preferred that the steam injected is in the range of from about the stoichiometric requirement to about 3 times the stoichiometric requirement.
In one embodiment, the enriched hydrogen product has a purity of at least 60%. In one embodiment, the H2:CO ratio of the enriched hydrogen product is in the range of from about 0.5:1 to about 1000:1. In some embodiments the enriched hydrogen product has a purity in the range of from about 70% to about 99.99%, at temperature in the range of from about 400-1000 C, and a pressure in the range of from about 1 to about 100 atmospheres.
The WGSR may be of a type selected from the group consisting of: fixed bed reactors, fluidized bed reactors, entrained flow reactors, moving bed reactors rotary kilns, or combinations thereof. Additionally, the calcinations step may be performed in a calcinations reactor of a type selected from the group consisting of: fixed bed reactors, fluidized bed reactors, entrained flow reactors, moving bed reactors rotary kilns, or combinations thereof.
In some embodiments, the WGSR does not have a catalyst disposed therein. As such the WGSR operates at a temperature in the range of from about 550-750 C, in the pressure range of from about 1 to about 60 atm, it is preferred that the WGSR reactor operate in a temperature range of from about 600-700 C and at a pressure in the range of from about 20 to about 30 atm. In some embodiments, the enriched hydrogen product is 99% pure when 3 times the stoichiometric steam requirement is used. At the stoichiometric steam requirement the process produces an enriched hydrogen product that is 90% pure. In another catalytic embodiment, the enriched hydrogen product has a H2/Co ration of at least 2.5 and a maximum sulfur (H2S/COS) concentration of less than 10 ppm using only the stoichiometric requirement of steam.
In some embodiments, a catalyst may be used in the WGSR. A suitable high temperature shift catalyst which may include: Fe, Cu, Co, Mo, W, Cs, Pt, Ph, Pd, and other precious metal catalysts or their oxides or sulfides or combinations thereof. Suitable supports for use with the foregoing high temperature shift catalysts include: Cr2O3, ZnO, MgO, ceria, alumina, silica, zirconia and combinations thereof.
A WGSR reactor with a catalyst operates in the temperature range of from about 550-750 C and at a pressure in the range of from about 1 to about 100 atm. It is preferred that the WGSR reactor operate in the temperature range of from about 600-700 C and at a pressure of from about 20 to about 30 amt. When a catalyst is used the enriched hydrogen product may achieve 99.99% purity when 3× the stoichiometric requirement of steam is used in the WGSR. The enriched hydrogen product may achieve 98% purity when the stoichiometric requirement of steam is used. Some embodiments may attain a purity of at least 80% with a maximum sulfur (H2S/COS) concentration of less than 10 ppm when 3× the stoichiometric requirement of steam is used and at least 70% purity with a maximum sulfur concentration of less than 1 ppm when the stoichiometric requirement of steam is used.
The process may also comprise the step of (e) recycling at least a portion of a product stream from a Fischer-Tropsch reactor, fed by the WGSR, so as to introduce a chemical species selected from the group consisting of: methane, C1-C4 hydrocarbons, CO, hydrogen and combinations thereof back into the WGSR.
In all embodiments, the CaO may have a surface area of at least 12.0 m2/g and a pore volume of at least 0.015 cm3/g, said CaO having a sorption capacity of at least about 70 grams of CO2 per kilogram of CaO.
The CaO may be provided in any usable form including, but not limited to, pellets, granules, fines, monoliths and combinations thereof. The CaO may be obtained by processing chicken eggshells.
Although the regeneration of CaO step may be performed any functional process, it is preferred that it is conducted by a process selected from the group consisting of: (a) calcining in the presence of steam and/or CO2 and/or H2 with O2, and/or synthesis gas with O2 and/or under partial vacuum or combinations thereof; (b) a process in which the heat is added to the calciner using steam and a combination of calciner fuel and oxidant; (c) a process in which the calciner fuel is H2 or natural gas or synthesis gas or coal or combinations thereof; (d) a process in which the oxidant is air or oxygen or combinations thereof; (e) a process in which heat is provided to the calciner directly or indirectly; (f) calciner reactor temperatures ranging from about 700-1100 C; and (a process for adjusting the calciner temperature by modifying the CaO to CaCO3 ratio in the calciner. The gas phase product from the calciner may comprise pure CO2 and could also contain trace amounts of H2S.
The disclosed embodiments also includes a process for producing hydrogen, comprising the steps of: (a) reforming a gaseous hydrocarbon fuel in the presence of CaO and steam to remove CO2, sulfur and halide contaminants in the form of H2S, COS and HX, where X is a halide, in a solid-phase calcium-containing product comprising CaCO3, CaS and CaX2, thereby producing a mixture of CO and hydrogen; (b) separating the solid-phase calcium-containing product from an enriched gaseous hydrogen product; and (c) regenerating the CaO by calcining the solid-phase calcium-containing product at a condition selected from the group consisting of: in the presence of steam, in the presence of CO2, in the presence of synthesis gas, in the presence of H2 and O2, under partial vacuum, and combinations thereof.
The gaseous fuel may be natural gas, C1-C4 hydrocarbons, or mixtures thereof. The reforming step may involve the introduction of CO2, so called dry reforming.
The reforming step may involve a reforming catalyst. Suitable reforming catalysts include those comprising: Ni, Pt, Rh, Pd, Ru, W, Mo, their oxide or carbides or sulfides. The reforming catalyst may use a support. Suitable supports for use with the foregoing reforming or pre-reforming catalysts include: alumina, silica, titania, zirconia, and combinations thereof. It is preferred that the reforming catalyst is sulfur intolerant.
The reforming operation may occur in a temperature range of from about 550 to about 750 C. and at a pressure in the range of from about 1 to about 60 atm. Preferably, it operates in the temperature range of from about 600 to about 70° C. and at a pressure in the range of from about 20 to about 30 atm.
The enriched hydrogen product produced may be as pure as 99.9% when 3× the stoichiometric requirement of steam is used and 95% pure when the stoichiometric requirement of steam is used.
This process may additionally comprise the step of: (d) recycling at least a portion of a product stream from a Fischer-Tropsch reactor, fed by the reformer, so as to introduce a chemical species selected from the group consisting of: methane, C1-C4 hydrocarbons, CO, hydrogen and combinations thereof back into the reformer.
In all embodiments, the CaO may have a surface area of at least 12.0 m2/g and a pore volume of at least 0.015 cm3/g, said CaO having a sorption capacity of at least about 70 grams of CO2 per kilogram of CaO.
The CaO may be provided in any usable form including, but not limited to, pellets, granules, fines, monoliths and combinations thereof. The CaO may be obtained by processing chicken eggshells.
When a catalyst is used the enriched hydrogen product may achieve 99.99% purity when 3× the stoichiometric requirement of steam is used. The enriched hydrogen product may achieve 98% purity when the stoichiometric requirement of steam is used. Some embodiments may attain a purity of at least 80% with a maximum sulfur (H2S/COS) concentration of less than 10 ppm when 3× the stoichiometric requirement of steam is used and at least 70% purity with a maximum sulfur concentration of less than 1 ppm when the stoichiometric requirement of steam is used. The process allows for a hydrogen purity of at least 80% with a maximum sulfur (H2S/COS) concentration of less than 10 ppm when 3× the stoichiometric requirement of steam is used and at least 70% purity with a maximum sulfur concentration of less than 1 ppm when the stoichiometric requirement of steam is used.
Another process of the disclosed embodiments for producing hydrogen, comprising the steps of: (a) at least partially oxidizing a fuel into a raw gas comprising CO, hydrogen, steam and sulfur and halide contaminants in the form of H2S, COS and HX, where X is a halide; (b) passing the raw gas through a water gas shift reactor (WGSR) into which CaO and steam are injected, the CaO reacting with the shifted gas to remove CO2, sulfur and halides in a solid-phase calcium-containing product comprising CaCO3, CaS and CaX2; (c) separating the solid-phase calcium-containing product from an enriched gaseous hydrogen product; and (d) regenerating the CaO by calcining the solid-phase calcium-containing product at a condition selected from the group consisting of: in the presence of steam, in the presence of CO2, in the presence of synthesis gas, in the presence of H2 and O2, under partial vacuum, and combinations thereof.
In all embodiments, the CaO may have a surface area of at least 12.0 m2/g and a pore volume of at least 0.015 cm3/g, said CaO having a sorption capacity of at least about 70 grams of CO2 per kilogram of CaO.
The CaO may be provided in any usable form including, but not limited to, pellets, granules, fine, monoliths and combinations thereof. The CaO may be obtained by processing chicken eggshells.
Although the steam may be injected into the WGSR in any functional quantity, it is preferred that the steam injected is in the range of from about the stoichiometric requirement to about 3 times the stoichiometric requirement.
The WGSR may be of a type selected from the group consisting of: fixed bed reactors, fluidized bed reactors, entrained flow reactors, moving bed reactors rotary kilns, or combinations thereof. Additionally, the calcinations step may be performed in a calcinations reactor of a type selected from the group consisting of: fixed bed reactors, fluidized bed reactors, entrained flow reactors, moving bed reactors rotary kilns, or combinations thereof.
In some embodiments, the WGSR does not have a catalyst disposed therein. As such the WGSR operates at a temperature in the range of from about 550-750 C, in the pressure range of from about 1 to about 60 atm, it is preferred that the WGSR reactor operate in a temperature range of from about 600-700 C and at a pressure in the range of from about 20 to about 30 atm. In some embodiments, the enriched hydrogen product is 99% pure when 3 times the stoichiometric steam requirement is used. At the stoichiometric steam requirement the process produces an enriched hydrogen product that is 90% pure. In another catalytic embodiment, the enriched hydrogen product has a H2/Co ratio of at least 2.5 and a maximum sulfur (H2S/COS) concentration of less than 10 ppm using only the stoichiometric requirement of steam.
In some embodiments, a catalyst may be used in the WGSR. A suitable high temperature shift catalyst which may include: Fe, Cu, Co, Mo, W, Cs, Pt, Ph, Pd, and other precious metal catalysts or their oxides or sulfides or combinations thereof. Suitable supports for use with the foregoing high temperature shift catalysts include: Cr2O3, ZnO, MgO, ceria, alumina, silica, zirconia and combinations thereof.
A WGSR reactor with a catalyst operates in the temperature range of from about 550-750 C and at a pressure in the range of from about 1 to about 100 atm. It is preferred that the WGSR reactor operate in the temperature range of from about 600-700 C and at a pressure of from about 20 to about 30 atm. When a catalyst is used the enriched hydrogen product may achieve 99.99% purity when 3× the stoichiometric requirement of steam is used in the WGSR. The enriched hydrogen product may achieve 98% purity when the stoichiometric requirement of steam is used. Some embodiments may attain a purity of at least 80% with a maximum sulfur (H2S/COS) concentration of less than 10 ppm when 3× the stoichiometric requirement of steam is used and at least 70% purity with a maximum sulfur concentration of less than 1 ppm when the stoichiometric requirement of steam is used.